Abstract
The mechanism of anodic oxidation of saturated hydrocarbons in fluorosulfuric acid has been established with cyclopentane and cyclohexane. Two monoelectronic transfers are separated by a chemical reaction which is a deprotonation: RH→[RH] ⋎++ e − E [RH] ⋎+→R ⋎+H + C R ⋎→R ++ e − E This ECE mechanism is supported by cyclic voltammetry and coulometries performed at cryogenic temperatures. It is shown that R is chemisorbed at low temperature: R radicals are hard and can give a complex with the platinum atoms of the anode which are also hard (because they are strongly deficient in electrons). Such a complex formation can explain why R is more difficult to oxidize than the parent hydrocarbon RH.
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